It has been known in the art for many years that certain highly crosslinked addition polymers such as those derived from styrene and divinylbenzene, and from (meth)acrylates and polyfunctional (meth)acrylates, when made under certain conditions, have very high surface areas and porosities. These polymers, sometimes called macroreticular polymers, are articles of commerce, for example those being sold by the Rohm and Haas Company under the tradename Amberlite, and in particular the Amberlite XAD series. Described in the next 7 paragraphs is some of the information published about macroreticular resins. More information may be found in the references cited.
An early report on macroreticular resins is that of R. Kunin, et. al., J. Am. Chem. Soc., vol. 84, pp. 305-306 (1962), in which it is reported that copolymers of styrene and divinylbenzene give polymers with high surface areas, mostly reported to be under 100 m.sup.2 /g. The apparent key to getting high surface areas is performing the polymerization in a good solvent for the monomers but a poor solvent for polymers.
K. A. Kun and R. Kunin in Polym. Lett., vol. 2, pp. 587-591 (1964), describe the structure of such macroreticular polymers as ". . . agglomerates of randomly packed microspheres with a continuous nongel pore structure similar to that found in bone char or alumina."
R. L. Gustafson, et al., Ind. Eng. Chem., Prod. Res. and Dev., vol. 7, pp. 107-115 (1968) further describe the adsorption properties of these styrene-divinylbenzene polymers, but in this paper several of the polymers have surface areas much greater than 100 m.sup.2 /g and porosities of 25% or more.
J. Paleos, J. Colloid Interface Sci., vol. 31, pp. 7-18 (1969) further describes adsorption by styrene divinylbenzene polymers, and also describes macroreticular polymers derived from acrylic monomers.
W. G. Rixey and C. J. King, J. Colloid Interface Sci., vol. 131, pp. 320-332 (1989) describe some surface area and porosity properties of the Amberlite resins.
A booklet published in 1985 by Rohm and Haas Co., Philadelphia, Pa., entitled "Catalysis by functionalized Porous Organic Polymers" has a useful review of macroreticular resins, both of their properties and historically.
U.S. Pat. No. 4,224,415 describes the preparation of macroreticular resins from acrylic and styrenic monomers, among others, in particular types of solvent systems. The solvent systems were necessary to produce the macroreticular resins. Other U.S. patents illustrating the synthesis of macroreticular resins, and the compositional range of monomers useful, include U.S. Pat. Nos. 4,221,871, 4,382,124, 3,663,467, 3,767,600 and 3,322,695. Most of these use basically the same type of technology described in U.S. Pat. No. 4,224,415.
In all of the above references cited, all of the polymers have flexibilizing groups (infra) resulting from the fact that they are formed by polymerization of vinyl monomers (polymerization of any vinyl monomer results in polymers with flexiblizing groups).
O. Ermer, in J. Am. Chem. Soc., vol. 110, pp. 3747-3754 (1988), describes the theoretical possibility of making polymers containing adamantane groups that would have interstities of fixed size, much like a zeolite. However, the discussion is purely theoretical, and no polymers are actually made. The compound used experimentally is a monomer that is held together by hydrogen bonding, not a polymer or resin.
B. F. Hoskins and R. Robson, J. Am. Chem. Soc., vol. 111, pp. 5962-5964 (1989), describe the preparation of a copper complex that is crystalline but has large adamantane-like cavities. It was speculated in a report on this paper in Chem. Eng. News, Jul. 31, 1989, p. 32 that such a structure may provide molecular sieve and ion-exchange properties. No mention is made of making similar organic polymers or resins.
S. M. Aharoni and S. F. Edwards in Macromol., vol. 22, pp. 3361-3374 (1989) describe gels made from rigid polyamide networks. Virtually all of the work described in this paper is done when the polymer is swollen with a solvent to form a gel. Dried gel particles were described as "highly ramified" but no mention is made of surface area or porosity.
I. Johannsen, et. al., Macromol., vol. 22, pp. 566-570 (1989) describe the polymerization of 1,3,5-triaminobenzene to give an air unstable highly crosslinked polymer. When polymerized over about 24 hr. the polymer is described as consisting of spheres 1-10 micrometers in diameter. No mention is made of high porosity or surface area.
P. A. Agaskar in J. Am. Chem. Soc., vol. 111, pp. 6858-6859 (1989) describes some macromolecules made from "vinyl functionalized spherosilicates." Although the material is described as being potentially microporous, after removal of solvent no microporosity was found experimentally.
U.S. Pat. No. 4,857,630 describes the preparation of highly branched, functionalized, wholly aromatic poly(arylenes). No mention is made of the surface area or porosity of these materials, and they are soluble in organic solvents.
U.S. Pat. No. 3,969,325 describes a process for the formation of a so-called "BBB" polymer with a high surface area, 100 to 500 m.sup.2 /g or more. No porosity of this polymer is reported in this patent. Although this polymer has no flexiblizing groups, it is reported elsewhere to be soluble in methanesulfonic acid.
It is the object of this invention to provide insoluble, high surface area and high porosity resins that contain little or no flexiblizing groups, for use as absorbants as for oil spills. A further object of this invention is to provide a method for the synthesis of such resins.